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Intrinsic Instability of Cs 2 In(I)M(III)X 6 (M = Bi, Sb; X = Halogen) Double Perovskites: A Combined Density Functional Theory and Experimental Study

Journal Article · · Journal of the American Chemical Society
DOI:https://doi.org/10.1021/jacs.7b02227· OSTI ID:1488933
 [1];  [2];  [3];  [4];  [2];  [1]
  1. Department of Physics and Astronomy and Wright Center for Photovoltaics Innovation and Commercialization, The University of Toledo, Toledo, Ohio 43606, United States
  2. Department of Mechanical Engineering and Materials Science, and Department of Chemistry, Duke University, Durham, North Carolina 27708, United States
  3. Department of Physics and Astronomy and Wright Center for Photovoltaics Innovation and Commercialization, The University of Toledo, Toledo, Ohio 43606, United States; School of Physics and Technology, Center for Electron Microscopy, MOE Key Laboratory of Artificial Micro- and Nano-structures, and Institute for Advanced Studies, Wuhan University, Wuhan 430072, China
  4. School of Physics and Technology, Center for Electron Microscopy, MOE Key Laboratory of Artificial Micro- and Nano-structures, and Institute for Advanced Studies, Wuhan University, Wuhan 430072, China
+ Show Author Affiliations
Recently, there has been substantial interest in developing double-B-cation halide perovskites, which hold the potential to overcome the toxicity and instability issues inherent within emerging lead halide-based solar absorber materials. Among all double perovskites investigated, In(I)-based Cs2InBiCl6 and Cs2InSbCl6 have been proposed as promising thin-film photovoltaic absorber candidates, with computational examination predicting suitable materials properties, including direct bandgap and small effective masses for both electrons and holes. In this study, we report the intrinsic instability of Cs2In(I)M(III)X6 (M = Bi, Sb; X = halogen) double perovskites by a combination of density functional theory and experimental study. Our results suggest that the In(I)-based double perovskites are unstable against oxidation into In(III)-based compounds. Further, the results show the need to consider reduction–oxidation (redox) chemistry when predicting stability of new prospective electronic materials, especially when less common oxidation states are involved.
Research Organization:
Lawrence Berkeley National Laboratory-National Energy Research Scientific Computing Center
Sponsoring Organization:
USDOE Office of Energy Efficiency and Renewable Energy (EERE)
Grant/Contract Number:
EE0006712; AC02-05CH11231
OSTI ID:
1488933
Alternate ID(s):
OSTI ID: 1559768
Journal Information:
Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 17 Vol. 139; ISSN 0002-7863
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

References (22)

Unique Properties of Halide Perovskites as Possible Origins of the Superior Solar Cell Performance journal May 2014
In3Ti2Br9: Jahn-Teller Unstable Indium(I) and Antiferromagnetically Coupled Titanium(III) Atoms journal May 1995
Thermodynamic Stability and Defect Chemistry of Bismuth-Based Lead-Free Double Perovskites journal August 2016
Zur Kenntnis der Chloro- und Bromo-Indate (III). A3In2Cl9 (A = Cs, Rb, In, Tl) und Cs3In2Br9?x Clx (x = 0, 3, 6, 7, 8) journal October 1978
Phase transitions in elpasolites (ordered perovskites) journal November 1998
Thin-Film Preparation and Characterization of Cs 3 Sb 2 I 9 : A Lead-Free Layered Perovskite Semiconductor journal August 2015
Crystal and Electronic Structures of Complex Bismuth Iodides A 3 Bi 2 I 9 ( A = K, Rb, Cs) Related to Perovskite: Aiding the Rational Design of Photovoltaics journal October 2015
Cs 2 AgBiX 6 (X = Br, Cl): New Visible Light Absorbing, Lead-Free Halide Perovskite Semiconductors journal February 2016
Rb as an Alternative Cation for Templating Inorganic Lead-Free Perovskites for Solution Processed Photovoltaics journal October 2016
Synthesis and Properties of a Lead-Free Hybrid Double Perovskite: (CH 3 NH 3 ) 2 AgBiBr 6 journal January 2017
Organic–Inorganic Perovskites: Structural Versatility for Functional Materials Design journal March 2016
Lead-Free Halide Double Perovskites via Heterovalent Substitution of Noble Metals journal March 2016
Cs 2 InAgCl 6 : A New Lead-Free Halide Double Perovskite with Direct Band Gap journal January 2017
Optoelectronic Properties of (CH 3 NH 3 ) 3 Sb 2 I 9 Thin Films for Photovoltaic Applications journal June 2016
Organometal Halide Perovskites as Visible-Light Sensitizers for Photovoltaic Cells journal May 2009
A Bismuth-Halide Double Perovskite with Long Carrier Recombination Lifetime for Photovoltaic Applications journal February 2016
Design of Lead-Free Inorganic Halide Perovskites for Solar Cells via Cation-Transmutation journal February 2017
Superior Photovoltaic Properties of Lead Halide Perovskites: Insights from First-Principles Theory journal February 2015
The synthesis, structure and electronic properties of a lead-free hybrid inorganic–organic double perovskite (MA) 2 KBiCl 6 (MA = methylammonium) journal January 2016
Searching for promising new perovskite-based photovoltaic absorbers: the importance of electronic dimensionality journal January 2017
Exploring the properties of lead-free hybrid double perovskites using a combined computational-experimental approach journal January 2016
The crystal structure of the room temperature modification of indium chloride, InCl journal November 1966

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Bandgap Engineering of Lead-Free Double Perovskite Cs 2 AgBiBr 6 through Trivalent Metal Alloying journal June 2017
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Low-Bandgap Cs 4 CuSb 2 Cl 12 Layered Double Perovskite: Synthesis, Reversible Thermal Changes, and Magnetic Interaction journal July 2018
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Systematic understanding of f ‐electron–based semiconducting actinide perovskites Ba 2 MgMO 6 (M = U, Np) from DFT ab initio calculations journal December 2019
Lead‐Free Double Perovskite Cs 2 SnX 6 : Facile Solution Synthesis and Excellent Stability journal August 2019
Structurally Stabilizing and Environment Friendly Triggers: Double‐Metallic Lead‐Free Perovskites journal May 2019
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Electronic and optical properties of lead-free hybrid double perovskites for photovoltaic and optoelectronic applications journal January 2019
Manipulation of cation combinations and configurations of halide double perovskites for solar cell absorbers journal January 2018
Initiation and future prospects of colloidal metal halide double-perovskite nanocrystals: Cs 2 AgBiX 6 (X = Cl, Br, I) journal January 2018
High-throughput computational design of organic–inorganic hybrid halide semiconductors beyond perovskites for optoelectronics journal January 2019
Advances in lead-free double perovskite nanocrystals, engineering band-gaps and enhancing stability through composition tunability journal January 2019
Lead-free double perovskites Cs 2 InCuCl 6 and (CH 3 NH 3 ) 2 InCuCl 6 : electronic, optical, and electrical properties journal January 2019
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Predicting the thermodynamic stability of double-perovskite halides from density functional theory journal August 2018
Controlled growth of SbSI thin films from amorphous Sb 2 S 3 for low-temperature solution processed chalcohalide solar cells journal December 2018
Pressure-induced semiconductor-to-metal phase transition of a charge-ordered indium halide perovskite journal November 2019
Cs 2 TlBiI 6 : a new lead-free halide double perovskite with direct band gap journal August 2019
Recent progress in Pb-free stable inorganic double halide perovskites journal July 2018
Optoelectronic Properties and Defect Physics of Lead-Free Photovoltaic Absorbers Cs 2 Au I Au III X 6 ( X = I , Br ) journal January 2020
Double perovskites overtaking the single perovskites: A set of new solar harvesting materials with much higher stability and efficiency journal May 2018
Lead-Free Halide Double Perovskites: A Review of the Structural, Optical, and Stability Properties as Well as Their Viability to Replace Lead Halide Perovskites journal August 2018
Double Perovskites overtaking the single perovskites : A set of new solar harvesting materials with much higher stability and efficiency text January 2018

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